10-hydrazono-3,7-dialkyl-2,6-decadienoates

ABSTRACT

NOVEL HYDRAZONO COMPOUNDS PREPARED BY THE REACTION OF A HYDRAZINE WITH AN ALIPHATIC UNSATURATED ALDEHYDE WHICH ARE USEFUL FOR THE CONTROL OF INSECTS.

United States Patent Olfice as... $173, 13:

3,732,262 ment and, in some cases, sterility and inability to re- 10-HYDRAZON0-3,7-DlALKYL-2,6- fi DECADIENOATES e compounds of Formula A are prepared according Clive A. Henrick and John B. Siddall, Palo Alto, Calif., to the followms Outlined y is:

assignors to Zoecon Corporation, Palo Alto, Calif. 5 H R1 0 N0 Drawing. Filed May 12, 1971, Ser. No. 142,818 I 1 g Q Int. Cl. C07c 109/14, 69/66; A01n 9/20 2 US. Cl. 260404.5 11 Claims R NNH2 ABSTRACT OF THE DISCLOSURE RA/ (H) Novel hydrazono compounds prepared by the reaction R3 R2 R1 0 of a hydrazine with an aliphatic unsaturated aldehyde l l l 4- WhlCh are useful for the control of insects. R N N CH CH2 UHF-643E CH2 COH J3 OR In the practice of the above outline synthesis, an alde- ThlS tnven relates to novel hydrazones f the hyde of Formula I is reacted with hydrazine of Formula preparation and use of the compounds. More particularly, II to yield the hydrazone compound f Formula In novel hydrazone unds of the presgil t lnven'tlon are carrying out the reaction, an excess of the hydrazine (l1) represented y the fonOWlng Formula is used. The reaction can be done neat or in the presence 3 R2 I'm an organic solvent, such as the lower monohydric R4-N N=CH CHT CHZ (520114313243H2 C=OH alcohols. In order to speed up the reaction, a trace of an (A) acid can be used to catalyze the reaction. The reaction can be carried out from about room temperature to rewherem flux and is usually complete within a few minutes to R is lower alkyl, cycloalkyl, aralkyl or aryl; several hours.

each of R and R is lower alkyl; The precursors of Formula I can be prepared as de- R is hydrogen or lower alkyl; and scribed in copending application Ser. No. 73,599, filed R is lower alkyl. or phenyl. Sept. 18, 1970, the disclosure of which is incorporated by reference.

The term lower alkyl as used harem refers to an The following examples are provided to illustrate the alkyl group, straight or branched, having a chain length of one to six carbon atoms. The term u y yLaa as present invention. Temperature is given in degrees centiused herein, refers to a cyclic alkyl group of four to eight grade EXAMPLE 1 carbon atoms. The term aralkyl, as used herein, refers to a monovalent group of seven to twelve carbon atoms in A miXture of 22 g. of methyl 9-carbonyl-3,7-dimethylwhich an aryl .group is substituted for a hydrocarbon nona-2,6-dienoate and 9.6 g. of isopropyl hydrazine atom of an alkyl group, such as benzyl, xylyl, mesityl, (98%) is prepared and then allowed to stand overnight phenylethyl, methylbenzyl, naphthylmethyl and napthylat room temperature. Then excess hydrazine is removed ethyl. The term aryl, as used herein, refers to monoby evaporation under reduced pressure. The crude hyvalent aryl group of six to twelve carbons, such as phenyl drazone product is purified by column chromatography nd naphthyl, to yield methyl 10-isopropylhydrazono-3,7-dimethyldeca- The compounds of Formula A are useful insect con- 2,6-dienoate.

CH3 1'1 0H3 (EH; 0

CHrN--N=CHCHz-CHZ(l=CHCH2-CH O=0 H-C- 0 CH3 CH3 trol agents. For application, the insect control agents of EXAMPLE 2 the present invention are applied using a suitable carrier To a mixture of 22 f methyl 1 7 substance, liquid or solid, such as talc, silica, cellulose, methylnona 2 6 dien0ate and L7 of methylhydrgzine syn he c and natural resins Water acetone Xylene and is added one ml. of acetic acid. The mixture is allowed mineral and vegetable oils. Generally, a formulation will to stand for about 16 hours and then excess methyl contain less than 95% of the insect control agent and drazine is removed by evaporation under reduced presmore frequently less than 25%. Sufficient application Sure The crude product is ifi d b chromatography 1 Should be .made to provide from i to 50 micro' yield methyl 9 meth'ylhydrazono 3,7 dimethyldeca-2,6- grams of msect control agent per msect based upon the dienoate estimated population. Typical insects which can be controlled by the present invention are members of Diptera, I Coleoptera, Homoptera, Herniptera, Lepidopteran and a-NN=CH-CHz-CH2-C=CHCHzCHz-C=CH-C-OOH Orthoptera, such as mosquitos, aphids, beetles, moths, The process of this example is repeated using dimeflwb roaches and graphasoma. Preferably, the msect control hydrazine in Place of methyl hydrazine to prepare methyl agent is apphed to Immature msect at the embryo 10-dimethylhydrazono-3,7 dimethyldeca-Z,6-dienoate.

larvae or pupae stage. Without any intention of being H CH3 CH 0 bound by theory, the insect control agents of the present EXAMPLE 3 invention, unlike conventional insecticides, are believed A mixture of 2.2 -g. of methyl 9-carbonyl-3,7-dimethylto be effective control agents by disrupting normal metanona-2,6-dienoate, 1.8 g. of ethylhydrazine and 10 m1. of

morphic development resulting in abnormal developdry methanol is prepared and then allowed to stand for about 18 hours at room temperature. Then the mixture is concentrated by evaporation under reduced pressure and the concentrate purified by chromatography to yield methyl 10-ethy1hydrazono-3,7-dimethyldeca-2,6-dienoate.

By following the procedure of Example 1, 2, or 3, methyl hydrazine is reacted with each of 1 ethyl 9-carbonyl-3,7-dimethylnona-2,6-dienoate,

isopropyl 9-carbonyl-3,7-dimethylnona-2,6-dienoate,

benzyl 9-carbonyl-3,7-dimethylnona-2,6-dienoate,

cyclohexyl 9carbonyl-3,7-dimethylnona-2,6-dienoate,

methyl 9-carbonyl-3-methyl-7-ethylnona-2,6-dienoate,

and

ethyl 9-carbonyl-3-methyl-7-ethylnona-2 ;6-dienoate to prepare:

Similarly, by reacting each of ethyl hydrazine, dimethylhydrazine and diethylhydrazine with each of the aldehydes enumerated in the preceding paragraph, the respective lethylhydrazono, IO-dimethylhydrazono and l0-diethylhydrazono derivatives are prepared, e.g.,

ethyl -ethylhydrazono-3,7-dimethyldeca-2,6-dienoate, ethyl l0-dimethylhydrazono-3,7-dimethyldeca-2,6-

dienoate, ethyl 10-diethylhydrazono-3,7-dimethyldeca-2,6-dianoate, isopropyl l0-ethylhydrazono-3,7-dimethyldeca-2,6-

dienoate, etc.

EXAMPLE 5 By use of the process of Example 1, 2 or 3, phenylhydrazine is reacted with each of methyl 9-carbonyl-3,7-dimethylnona-2,6-dienoate, ethyl 9-carbonyl-3,7-dimethylnona-2,6-dienoate, methyl 9-carbonyl-3-methyl-7-ethylnona-2,6-dienoate, and methyl 9-carbonyl-3,7-diethylnona- 2,6-dienoate to prepare methyl 10-phenylhydrazono-3,7- dimethyldeca-2,6-dienoate, ethyl l0-phenylhydrazono-3,7- dimethyldeca-2,6-dienoate, methyl 10-phenylhydrazono-3- methyl-7-ethyldeca-2,6-dienoate, and methyl IO-phenylhydrazono-3,7-diethyldeca-2,6-dienoate, respectively.

What is claimed is:

1. A compound selected from those of the following Formula A:

(A) wherein,

R is lower alkyl, cycloalkyl, aralkyl or aryl;

each of R and R is lower alkyl;

R is hydrogen or lower alkyl; and

R is lower alkyl or phenyl.

2. A compound according to claim 1 wherein each of R and R is methyl or ethyl and R is lower alkyl.

3. A compound according to claim 2 wherein R is methyl, R is hydrogen or lower alkyl and R is lower alkyl.

4. A compound according to claim 3 wherein R is hydrogen.

5. A compound according to claim 4 wherein R is methyl or ethyl.

6. A compound according to claim 3 wherein each of R and R is methyl or ethyl.

7. A compound according to claim 5 wherein R is methyl, ethyl or isopropyl.

8. A compound according to claim 6 wherein R is methyl, ethyl or isopropyl.

9. A compound according to claim 1 wherein R is lower alkyl; R is methyl; R is methyl or ethyl; R is hydrogen; and R is phenyl.

10. A compound according to claim 9 wherein R is methyl or ethyl.

11. The compound, ethyl 10-dimethylhydrazono-S,7- dirnethyldeca-Z,6-dienoate, according to claim 8.

References Cited Meinwald et al.: Tetrahedron Letters, No. 47, pp. 4893-96 (1968).

LEWIS GO'ITS, Primary Examiner D. G. RIVERS, Assistant Examiner US. Cl. X.R.

260-4109 R; 424-312, DIG. 12, 309 

